US20220344573A1 - Polymer-based piezoelectric composite material film - Google Patents

Polymer-based piezoelectric composite material film Download PDF

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US20220344573A1
US20220344573A1 US17/863,703 US202217863703A US2022344573A1 US 20220344573 A1 US20220344573 A1 US 20220344573A1 US 202217863703 A US202217863703 A US 202217863703A US 2022344573 A1 US2022344573 A1 US 2022344573A1
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piezoelectric
polymer
composite material
film
piezoelectric composite
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Masayuki HAGA
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Fujifilm Corp
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    • H01L41/183—
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00—Piezoelectric transducers; Electrostrictive transducers
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00—Piezoelectric transducers; Electrostrictive transducers
    • H04R17/005—Piezoelectric transducers; Electrostrictive transducers using a piezoelectric polymer
    • H01L41/37—
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
    • H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
    • H10N30/084—Shaping or machining of piezoelectric or electrostrictive bodies by moulding or extrusion
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/092—Forming composite materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2499/00—Aspects covered by H04R or H04S not otherwise provided for in their subgroups
    • H04R2499/10—General applications
    • H04R2499/15—Transducers incorporated in visual displaying devices, e.g. televisions, computer displays, laptops
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/88—Mounts; Supports; Enclosures; Casings
    • H10N30/883—Additional insulation means preventing electrical, physical or chemical damage, e.g. protective coatings

Definitions

  • the present invention relates to a polymer-based piezoelectric composite material film used for an acoustic device such as a speaker.
  • speakers used in these thin displays are also required to be lighter and thinner.
  • flexible displays formed of flexible substrates such as plastics speakers used in the flexible displays are also required to be flexible.
  • Examples of typical shapes of speakers of the related art include a funnel-like so-called cone shape and a spherical dome shape.
  • a funnel-like so-called cone shape and a spherical dome shape.
  • the lightness and the flexibility of the speaker are impaired because the speaker cannot be sufficiently made thin.
  • the speaker is attached externally, it is troublesome to carry the speaker.
  • the electroacoustic piezoelectric film disclosed in WO2017/018313A includes a polymer-based piezoelectric composite material (piezoelectric layer) obtained by dispersing piezoelectric particles in a viscoelastic matrix consisting of a polymer material having a viscoelasticity at room temperature, an electrode layer formed on each of both surfaces of the polymer-based piezoelectric composite material, and a protective layer formed on a surface of the electrode layer.
  • a ferroelectric material such as lead zirconate titanate (PZT) is used as the piezoelectric particles.
  • the crystal structure of the ferroelectric material is divided into a plurality of domains in which directions of spontaneous polarization are different from each other. In this state, since the spontaneous polarization of each domain and the piezoelectric effect produced by the spontaneous polarization cancel each other out, the piezoelectricity is not seen in the entire structure.
  • the directions of spontaneous polarization of each domain are arranged (aligned) by performing an electric polarization treatment such as corona poling and applying an electric field of a certain value or greater from the outside.
  • the piezoelectric particles subjected to the electrical polarization treatment exhibit a piezoelectric effect in response to the electric field from the outside.
  • the piezoelectric layer of the polymer-based piezoelectric composite material film contains such piezoelectric particles having piezoelectricity, the piezoelectric film stretches and contracts in the plane direction and vibrates in a direction perpendicular to the plane in response to the applied voltage so that the vibration (sound) is converted to an electric signal.
  • X-ray diffraction method has been used as a method of analyzing a crystal structure, and XRD is used to investigate how the atoms are arranged inside a crystal.
  • An object of the present invention is to solve such a problem of the related art and to provide a polymer-based piezoelectric composite material film which has high conversion efficiency and is capable of reproducing a sound with a sufficient volume.
  • the present invention has the following configurations.
  • FIG. 1 is a cross-sectional view conceptually illustrating an example of a polymer-based piezoelectric composite material film according to the embodiment of the present invention.
  • FIG. 2 is a conceptual view for describing an example of a method of preparing a polymer-based piezoelectric composite material film.
  • FIG. 3 is a conceptual view for describing an example of a method of preparing a polymer-based piezoelectric composite material film.
  • FIG. 4 is a conceptual view for describing an example of a method of preparing a polymer-based piezoelectric composite material film.
  • FIG. 5 is a conceptual view for describing an example of a method of preparing a polymer-based piezoelectric composite material film.
  • a numerical range shown using “to” indicates a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • FIG. 1 is a cross-sectional view conceptually illustrating an example of the polymer-based piezoelectric composite material film according to the embodiment of the present invention.
  • the polymer-based piezoelectric composite material film (hereinafter, also referred to as a piezoelectric film) 10 includes a polymer-based piezoelectric composite material 12 containing piezoelectric particles 26 in a matrix 24 that contains a polymer material, a lower electrode 14 laminated on one surface of the polymer-based piezoelectric composite material 12 , a lower protective layer 18 laminated on the lower electrode 14 , an upper electrode 16 laminated on the other surface of the polymer-based piezoelectric composite material 12 , and an upper protective layer 20 laminated on the upper electrode 16 .
  • the polymer-based piezoelectric composite material is a sheet-like material having piezoelectricity.
  • the polymer-based piezoelectric composite material is also referred to as a piezoelectric layer.
  • the coefficient of variation of “intensity ratio ⁇ 1 of (002) plane peak intensity and (200) plane peak intensity derived from piezoelectric particles (002) plane peak intensity/((002) plane peak intensity+(200) plane peak intensity)” in a case where the piezoelectric layer 12 consisting of the polymer-based piezoelectric composite material is evaluated by the X-ray diffraction method is less than 0.3.
  • the intensity ratio ⁇ 1 is preferably 0.6 or greater and less than 1.
  • the piezoelectric layer 12 illustrated in FIG. 1 contains the piezoelectric particles 26 in the matrix 24 containing a polymer material. Further, the lower electrode 14 and the upper electrode 16 are electrode layers in the present invention. Further, the lower protective layer 18 and the upper protective layer 20 are protective layers in the present invention.
  • the piezoelectric film 10 (piezoelectric layer 12 ) is polarized in the thickness direction as a preferred embodiment.
  • the piezoelectric layer 12 which is a polymer-based piezoelectric composite material consists of a polymer-based piezoelectric composite material obtained by uniformly dispersing the piezoelectric particles 26 in the matrix 24 consisting of a polymer material as conceptually illustrated in FIG. 1 .
  • the material of the matrix 24 (serving as a matrix and a binder) of the polymer-based piezoelectric composite material constituting the piezoelectric layer 12 a polymer material having viscoelasticity at room temperature is preferably used. Further, in the present specification, the “room temperature” indicates a temperature range of approximately 0° C. to 50° C.
  • the piezoelectric film 10 according to the embodiment of the present invention is suitably used for a speaker having flexibility such as a speaker for a flexible display.
  • the polymer-based piezoelectric composite material (piezoelectric layer 12 ) used for a speaker having flexibility satisfies the following requirements. Therefore, it is preferable that a polymer material having viscoelasticity at room temperature is used as a material satisfying the following requirements.
  • the piezoelectric film is continuously subjected to large bending deformation from the outside at a relatively slow vibration of less than or equal to a few Hz.
  • a relatively slow vibration of less than or equal to a few Hz.
  • the polymer-based piezoelectric composite material is hard, a large bending stress is generated to that extent, and a crack is generated at the interface between a matrix and piezoelectric particles, which may lead to breakage.
  • the polymer-based piezoelectric composite material is required to have suitable flexibility.
  • strain energy is diffused into the outside as heat, the stress is able to be relieved. Therefore, the polymer-based piezoelectric composite material is required to have a suitably large loss tangent.
  • the piezoelectric particles vibrate at a frequency of an audio band of 20 Hz to 20 kHz, and the vibration energy causes the entire polymer-based piezoelectric composite material (piezoelectric layer) to vibrate integrally so that a sound is reproduced. Therefore, in order to increase the transmission efficiency of the vibration energy, the polymer-based piezoelectric composite material is required to have appropriate hardness. In addition, in a case where the frequencies of the speaker are smooth as the frequency characteristic thereof, an amount of change in acoustic quality in a case where the lowest resonance frequency is changed in association with a change in the curvature of the speaker decreases. Therefore, the loss tangent of the polymer-based piezoelectric composite material is required to be suitably large.
  • the polymer-based piezoelectric composite material is required to exhibit a behavior of being rigid with respect to a vibration of 20 Hz to 20 kHz and being flexible with respect to a vibration of less than or equal to a few Hz.
  • the loss tangent of a polymer-based piezoelectric composite material is required to be suitably large with respect to the vibration of all frequencies of 20 kHz or less.
  • a polymer solid has a viscoelasticity relieving mechanism, and a molecular movement having a large scale is observed as a decrease (relief) in a storage elastic modulus (Young's modulus) or a maximal value (absorption) in a loss elastic modulus along with an increase in temperature or a decrease in frequency.
  • the relief due to a microbrown movement of a molecular chain in an amorphous region is referred to as main dispersion, and an extremely large relieving phenomenon is observed.
  • a temperature at which this main dispersion occurs is a glass transition point (Tg), and the viscoelasticity relieving mechanism is most remarkably observed.
  • the polymer-based piezoelectric composite material exhibiting a behavior of being rigid with respect to a vibration of 20 Hz to 20 kHz and being flexible with respect to a vibration of less than or equal to a few Hz is realized by using a polymer material whose glass transition point is room temperature, that is, a polymer material having a viscoelasticity at room temperature as a matrix.
  • a polymer material in which the glass transition temperature at a frequency of 1 Hz is at room temperature, that is, in a range of 0° C. to 50° C. is used for a matrix of the polymer-based piezoelectric composite material.
  • the polymer material having a viscoelasticity at room temperature various known materials can be used as long as the materials have dielectric properties. It is preferable that a polymer material in which the maximal value of a loss tangent at a frequency of 1 Hz according to a dynamic viscoelasticity test at room temperature, that is, in a range of 0° C. to 50° C. is 0.5 or greater is used as the polymer material.
  • a storage elastic modulus (E′) at a frequency of 1 Hz according to the dynamic viscoelasticity measurement is 100 MPa or greater at 0° C. and 10 MPa or less at 50° C.
  • the bending moment generated in a case where the polymer-based piezoelectric composite material is slowly bent due to the external force can be reduced, and the polymer-based piezoelectric composite material can exhibit a behavior of being rigid with respect to an acoustic vibration of 20 Hz to 20 kHz.
  • the relative dielectric constant of the polymer material is 10 or greater at 25° C. Accordingly, in a case where a voltage is applied to the polymer-based piezoelectric composite material, a higher electric field is applied to the piezoelectric particles in the matrix, and thus a large deformation amount can be expected.
  • the relative dielectric constant of the polymer material is 10 or less at 25° C.
  • polymer material satisfying such conditions examples include cyanoethylated polyvinyl alcohol (cyanoethylated PVA), polyvinyl acetate, polyvinylidene chloride-co-acrylonitrile, a polystyrene-vinyl polyisoprene block copolymer, polyvinyl methyl ketone, and polybutyl methacrylate.
  • cyanoethylated polyvinyl alcohol cyanoethylated PVA
  • polyvinyl acetate polyvinylidene chloride-co-acrylonitrile
  • a polystyrene-vinyl polyisoprene block copolymer polyvinyl methyl ketone
  • polybutyl methacrylate examples include cyanoethylated polyvinyl alcohol (cyanoethylated PVA), polyvinyl acetate, polyvinylidene chloride-co-acrylonitrile, a polystyrene-viny
  • these polymer materials may be used alone or in combination (mixture) of a plurality of kinds thereof.
  • a plurality of polymer materials may be used in combination as necessary.
  • dielectric polymer materials may be added to the matrix 24 in addition to the polymer material having viscoelasticity at room temperature as necessary.
  • dielectric polymer material examples include a fluorine-based polymer such as polyvinylidene fluoride, a vinylidene fluoride-tetrafluoroethylene copolymer, a vinylidene fluoride-trifluoroethylene copolymer, a polyvinylidene fluoride-trifluoroethylene copolymer, or a polyvinylidene fluoride-tetrafluoroethylene copolymer, a polymer containing a cyano group or a cyanoethyl group such as a vinylidene cyanide-vinyl acetate copolymer, cyanoethyl cellulose, cyanoethyl hydroxysaccharose, cyanoethyl hydroxycellulose, cyanoethyl hydroxypullulan, cyanoethyl methacrylate, cyanoethyl acrylate, cyanoethyl hydroxyethy
  • a polymer material containing a cyanoethyl group is suitably used.
  • the number of kinds of the dielectric polymer materials to be added in addition to the polymer material having viscoelasticity at room temperature such as cyanoethylated PVA is not limited to one, and a plurality of kinds of the materials may be added.
  • thermoplastic resin such as a vinyl chloride resin, polyethylene, polystyrene, a methacrylic resin, polybutene, or isobutylene
  • thermosetting resin such as a phenol resin, a urea resin, a melamine resin, an alkyd resin, or mica
  • a viscosity imparting agent such as rosin ester, rosin, terpene, terpene phenol, or a petroleum resin may be added.
  • the addition amount in a case of adding materials other than the polymer material having viscoelasticity such as cyanoethylated PVA is not particularly limited, but is preferably set to 30% by mass or less in terms of the proportion of the materials in the matrix 24 .
  • the characteristics of the polymer material to be added can be exhibited without impairing the viscoelasticity relieving mechanism in the matrix 24 , and thus preferable results, for example, an increase in the dielectric constant, improvement of the heat resistance, and improvement of the adhesiveness between the piezoelectric particles 26 and the electrode layer can be obtained.
  • the piezoelectric layer 12 is a polymer-based piezoelectric composite material which contains the piezoelectric particles 26 in the matrix 24 .
  • the piezoelectric particles 26 consist of ceramic particles having a perovskite type or wurtzite type crystal structure.
  • Ceramic particles constituting the piezoelectric particles 26 include lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), barium titanate (BaTiO 3 ), zinc oxide (ZnO), and a solid solution (BFBT) of barium titanate and bismuth ferrite (BiFe 3 ).
  • PZT lead zirconate titanate
  • PLAT lead lanthanum zirconate titanate
  • BaTiO 3 barium titanate
  • ZnO zinc oxide
  • BFBT solid solution of barium titanate and bismuth ferrite
  • the piezoelectric particles 26 may be used alone or in combination (mixture) of a plurality of kinds thereof.
  • the particle diameter of such piezoelectric particles 26 is not limited, and may be appropriately selected depending on the size, the applications, and the like of the polymer-based piezoelectric composite material (piezoelectric film 10 ).
  • the particle diameter of the piezoelectric particles 26 is preferably in a range of 1 to 10 ⁇ m. By setting the particle diameter of the piezoelectric particles 26 to be in the above-described range, preferable results in terms of achieving both excellent piezoelectric characteristics and flexibility of the polymer-based piezoelectric composite material (piezoelectric film 10 ) can be obtained.
  • the piezoelectric particles 26 in the piezoelectric layer 12 are uniformly dispersed in the matrix 24 with regularity, but the present invention is not limited thereto.
  • the piezoelectric particles 26 in the piezoelectric layer 12 may be irregularly dispersed in the matrix 24 as long as the piezoelectric particles 26 are preferably uniformly dispersed therein.
  • the ratio between the amount of the matrix 24 and the amount of the piezoelectric particles 26 in the piezoelectric layer 12 is not limited, and the ratio thereof may be appropriately set according to the size and the thickness of the piezoelectric layer 12 in the plane direction, the applications of the polymer-based piezoelectric composite material, the characteristics required for the polymer-based piezoelectric composite material, and the like.
  • the volume fraction of the piezoelectric particles 26 in the piezoelectric layer 12 is preferably in a range of 30% to 80%, more preferably 50% or greater, and still more preferably in a range of 50% to 80%.
  • the thickness of the piezoelectric layer 12 is not limited, and may be appropriately set according to the applications of the polymer-based piezoelectric composite material, the characteristics required for the polymer-based piezoelectric composite material, and the like. It is advantageous that the thickness of the piezoelectric layer 12 increases in terms of the rigidity such as the strength of stiffness of a so-called sheet-like material, but the voltage (potential difference) required to stretch and contract the piezoelectric layer 12 by the same amount increases.
  • the thickness of the piezoelectric layer 12 is preferably in a range of 10 to 300 ⁇ m, more preferably in a range of 20 to 200 ⁇ m, and still more preferably in a range of 30 to 150 ⁇ m.
  • the thickness of the piezoelectric layer 12 By setting the thickness of the piezoelectric layer 12 to be in the above-described range, preferable results in terms of achieving both ensuring of the rigidity and moderate elasticity can be obtained.
  • the piezoelectric film 10 of the illustrated example has a configuration in which the lower electrode 14 is provided on one surface of the piezoelectric layer 12 , the lower protective layer 28 is provided on the surface thereof, the upper electrode 16 is provided on the other surface of the piezoelectric layer 12 , and the upper protective layer 30 is provided on the surface thereof.
  • the upper electrode 16 and the lower electrode 14 form an electrode pair.
  • the piezoelectric film 10 has a configuration in which both surfaces of the piezoelectric layer 12 are sandwiched between the electrode pair, that is, the upper electrode 16 and the lower electrode 14 and the laminate is further sandwiched between the lower protective layer 28 and the upper protective layer 30 .
  • the region sandwiched between the upper electrode 16 and the lower electrode 14 is stretched and contracted according to an applied voltage.
  • the lower protective layer 28 and the upper protective layer 30 have a function of coating the upper electrode 16 and the lower electrode 14 and applying moderate rigidity and mechanical strength to the piezoelectric layer 12 . That is, the piezoelectric layer 12 consisting of the matrix 24 and the piezoelectric particles 26 in the piezoelectric film 10 exhibits extremely excellent flexibility under bending deformation at a slow vibration, but may have insufficient rigidity or mechanical strength depending on the applications. As a compensation for this, the piezoelectric film 10 is provided with the lower protective layer 28 and the upper protective layer 30 .
  • the lower protective layer 28 and the upper protective layer 30 are not limited, and various sheet-like materials can be used, and suitable examples thereof include various resin films.
  • a resin film consisting of polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), polycarbonate (PC), polyphenylene sulfide (PPS), polymethylmethacrylate (PMMA), polyetherimide (PEI), polyimide (PI), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), and a cyclic olefin-based resin is suitably used.
  • PET polyethylene terephthalate
  • PP polypropylene
  • PS polystyrene
  • PC polycarbonate
  • PPS polyphenylene sulfide
  • PMMA polymethylmethacrylate
  • PEI polyetherimide
  • PI polyimide
  • PEN polyethylene naphthalate
  • TAC triacetyl cellulose
  • a cyclic olefin-based resin is suitably used.
  • the thickness of the lower protective layer 28 or the upper protective layer 30 is not limited. In addition, the thicknesses of the lower protective layer 28 and the upper protective layer 30 are basically the same as each other, but may be different from each other.
  • the thickness of the lower protective layer 28 and the thickness of the upper protective layer 30 decrease except for the case where the mechanical strength or excellent handleability as a sheet-like material is required.
  • the thickness of the lower protective layer 28 and the upper protective layer 30 is preferably in a range of 3 ⁇ m to 100 ⁇ m, more preferably in a range of 3 ⁇ m to 50 ⁇ m, still more preferably in a range of 3 ⁇ m to 30 ⁇ m, and particularly preferably in a range of 4 ⁇ m to 10 ⁇ m.
  • the thickness of the lower protective layer 28 and the upper protective layer 30 in the piezoelectric film 10 is two times or less the thickness of the piezoelectric layer 12 , preferable results in terms of achieving both ensuring of the rigidity and moderate elasticity can be obtained.
  • the thickness of each of the lower protective layer 28 and the upper protective layer 30 is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 25 ⁇ m or less.
  • the lower electrode 14 is formed between the piezoelectric layer 12 and the lower protective layer 28
  • the upper electrode 16 is formed between the piezoelectric layer 12 and the upper protective layer 30 .
  • the lower electrode 14 and the upper electrode 16 are provided to apply a driving voltage to the piezoelectric layer 12 .
  • the material for forming the lower electrode 14 and the upper electrode 16 is not limited, and various conductors can be used as the material. Specific examples thereof include carbon, palladium, iron, tin, aluminum, nickel, platinum, gold, silver, copper, titanium, chromium, and molybdenum, alloys thereof, laminates and composites of these metals and alloys, and indium tin oxide. Among these, copper, aluminum, gold, silver, platinum, and indium tin oxide are suitably exemplified as the lower electrode 14 and the upper electrode 16 .
  • the method of forming the lower electrode 14 and the upper electrode 16 is not limited, and various known methods such as a vapor-phase deposition method (a vacuum film forming method) such as vacuum vapor deposition or sputtering, film formation using plating, and a method of bonding a foil formed of the materials described above can be used.
  • a vapor-phase deposition method a vacuum film forming method
  • sputtering a vacuum vapor deposition or sputtering
  • film formation using plating a method of bonding a foil formed of the materials described above
  • a thin film made of copper, aluminum, or the like formed by vacuum vapor deposition is suitably used as the lower electrode 14 and the upper electrode 16 .
  • a thin film made of copper formed by vacuum vapor deposition is suitably used.
  • the thickness of the lower electrode 14 and the upper electrode 16 is not limited. In addition, the thicknesses of the lower electrode 14 and the upper electrode 16 are basically the same as each other, but may be different from each other.
  • the thicknesses of lower electrode 14 and the upper electrode 16 decrease in a case where the electric resistance is not excessively high. That is, it is preferable that the lower electrode 14 and the upper electrode 16 are thin film electrodes.
  • each of the lower electrode 14 and the upper electrode 16 is less than the thickness of the protective layer, and is preferably in a range of 0.05 ⁇ m to 10 ⁇ m, more preferably in a range of 0.05 ⁇ m to 5 ⁇ m, still more preferably in a range of 0.08 ⁇ m to 3 ⁇ m, and particularly preferably in a range of 0.1 ⁇ m to 2 ⁇ m.
  • the product of the thicknesses of the lower electrode 14 and the upper electrode 16 and the Young's modulus of the piezoelectric film 10 is less than the product of the thicknesses of the lower protective layer 28 and the upper protective layer 30 and the Young's modulus because the flexibility is not considerably impaired.
  • the thickness of the lower electrode 14 and the upper electrode 16 is preferably 1.2 ⁇ m or less, more preferably 0.3 ⁇ m or less, and still more preferably 0.1 ⁇ m or less in a case of assuming that the thickness of the lower protective layer 28 and the upper protective layer 30 is 25 ⁇ m.
  • the maximal value of the loss tangent (tan ⁇ ) at a frequency of 1 Hz according to dynamic viscoelasticity measurement is present at room temperature and more preferable that the maximal value at which the loss tangent is 0.1 or greater is present at room temperature.
  • the storage elastic modulus (E′) at a frequency of 1 Hz according to the dynamic viscoelasticity measurement is in a range of 10 GPa to 30 GPa at 0° C. and in a range of 1 GPa to 10 GPa at 50° C. The same applies to the conditions for the piezoelectric layer 12 .
  • the piezoelectric film 10 may have large frequency dispersion in the storage elastic modulus (E′). That is, the piezoelectric film 10 can exhibit a behavior of being rigid with respect to a vibration of 20 Hz to 20 kHz and being flexible with respect to a vibration of less than or equal to a few Hz.
  • the product of the thickness and the storage elastic modulus at a frequency of 1 Hz according to the dynamic viscoelasticity measurement is in a range of 1.0 ⁇ 10 5 to 2.0 ⁇ 10 6 (1.0E+05 to 2.0E+06) N/m at 0° C. and in a range of 1.0 ⁇ 10 5 to 1.0 ⁇ 10 6 (1.0E+05 to 1.0E+06) N/m at 50° C.
  • the piezoelectric film 10 may have moderate rigidity and mechanical strength within a range not impairing the flexibility and the acoustic characteristics.
  • the loss tangent at a frequency of 1 kHz at 25° C. is 0.05 or greater in a master curve obtained from the dynamic viscoelasticity measurement. The same applies to the conditions for the piezoelectric layer 12 .
  • the frequency of a speaker using the piezoelectric film 10 is smooth as the frequency characteristic thereof, and thus a change in acoustic quality in a case where the lowest resonance frequency f 0 is changed according to a change in the curvature of the speaker can be decreased.
  • the storage elastic modulus (Young's modulus) and the loss tangent of the piezoelectric film 10 , the piezoelectric layer 12 , and the like may be measured by a known method.
  • the measurement may be performed using a dynamic viscoelasticity measuring device DMS6100 (manufactured by SII Nanotechnology Inc.).
  • Examples of the measurement conditions include a measurement frequency of 0.1 Hz to 20 Hz (0.1 Hz, 0.2 Hz, 0.5 Hz, 1 Hz, 2 Hz, 5 Hz, 10 Hz, and 20 Hz), a measurement temperature of ⁇ 50° C. to 150° C., a temperature rising rate of 2° C./min (in a nitrogen atmosphere), a sample size of 40 mm ⁇ 10 mm (including the clamped region), and a chuck-to-chuck distance of 20 mm.
  • the piezoelectric film 10 may further include an electrode lead-out portion that leads out the electrodes from the upper electrode 16 and the lower electrode 14 , and an insulating layer which covers a region where the piezoelectric layer 12 is exposed for preventing a short circuit or the like, in addition to the piezoelectric layer, the electrode layer, and the protective layer.
  • the electrode lead-out portion may be an electrode lead-out portion configured such that a portion where the electrode layer and the protective layer project convexly outside the piezoelectric layer in the plane direction is provided or configured such that a part of the protective layer is removed to form a hole portion, and a conductive material such as silver paste is inserted into the hole portion so that the conductive material is electrically conducted with the electrode layer.
  • each electrode layer may have two or more electrode lead-out portions.
  • the thin film electrode has three or more electrode lead-out portions in order to more reliably ensure the conduction.
  • the coefficient of variation of “intensity ratio ⁇ 1 of (002) plane peak intensity and (200) plane peak intensity derived from piezoelectric particles (002) plane peak intensity/((002) plane peak intensity+(200) plane peak intensity)” in a case where the polymer-based piezoelectric composite material which is the piezoelectric layer 12 is evaluated by the X-ray diffraction method is less than 0.3.
  • a ferroelectric material such as PZT is used as the piezoelectric particles.
  • the crystal structure of the ferroelectric material is divided into a plurality of domains in which directions of spontaneous polarization are different from each other. In this state, since the spontaneous polarization of each domain and the piezoelectric effect produced by the spontaneous polarization cancel each other out, the piezoelectricity is not seen in the entire structure.
  • the directions of spontaneous polarization of each domain are aligned by performing an electric polarization treatment such as corona poling to the piezoelectric layer and applying an electric field of a certain value or greater from the outside.
  • the piezoelectric particles subjected to the electrical polarization treatment exhibit a piezoelectric effect in response to the electric field from the outside.
  • the piezoelectric film stretches and contracts in the plane direction and vibrates in a direction perpendicular to the plane in response to the applied voltage so that the polymer-based piezoelectric composite material film converts the vibration (sound) to an electric signal.
  • the directions of spontaneous polarization of each domain of the crystal structure of the ferroelectric material are oriented in various directions such as the plane direction as well as the thickness direction of the piezoelectric film. Therefore, for example, even in a case where the electric polarization treatment is performed by applying a higher voltage, it is not possible to direct all the directions of the domains oriented in the plane direction, to the thickness direction in which an electric field is applied. In other words, the 90° domain cannot be completely removed.
  • the directions of the domains are oriented in various directions, and thus a variation in aligning properties of the domains is significant.
  • higher piezoelectricity cannot be obtained.
  • X-ray diffraction method has been used as a method of analyzing the crystal structure of such a piezoelectric layer (piezoelectric particles), and XRD is used to investigate how the atoms are arranged inside a crystal.
  • the (002) plane peak intensity is a tetragonal peak around 43.5° in an XRD pattern obtained by XRD analysis
  • the (200) plane peak intensity is a tetragonal peak around 45° in the XRD pattern obtained by XRD analysis.
  • the XRD analysis can be performed using an X-ray diffractometer (SmartLab, manufactured by Rigaku Corporation) or the like.
  • the (002) plane peak intensity corresponds to the proportion of the domains (c domains) of the piezoelectric film in the thickness direction
  • the (200) plane peak intensity corresponds to the proportion of the domains (a domains) in the plane direction of the piezoelectric film.
  • the coefficient of variation of the intensity ratio ⁇ 1 of the (002) plane peak intensity and the (200) plane peak intensity derived from piezoelectric particles in a case where the polymer-based piezoelectric composite material which is the piezoelectric layer 12 is evaluated by the X-ray diffraction method is less than 0.3. That is, the variation in aligning properties of domains is small. In the piezoelectric film formed of a piezoelectric layer in which the variation in the aligning properties of domains is small and the orientations of the domains are arranged, higher piezoelectricity can be obtained.
  • the piezoelectric film according to the embodiment of the present invention can increase, for example, the conversion efficiency between vibration (sound) and an electric signal, and a sound with a sufficient volume can be reproduced in a case where the piezoelectric film is used as a vibration plate of a speaker. Further, the conversion efficiency is high, and thus the power consumption can be reduced.
  • the coefficient of variation of the intensity ratio ⁇ 1 may be calculated by measuring optional five points of the intensity ratios ⁇ 1 with an interval of 10 mm or greater in the plane direction (direction perpendicular to the thickness direction) of the piezoelectric layer according to the above-described X-ray diffraction method (XRD), calculating the average value and the standard deviation thereof, and dividing the standard deviation by the average value.
  • XRD X-ray diffraction method
  • the intensity ratio ⁇ 1 of the (002) plane peak intensity and the (200) plane peak intensity derived from piezoelectric particles in a case where the polymer-based piezoelectric composite material is evaluated by the X-ray diffraction method is preferably 0.6 or greater and less than 1 and more preferably in a range of 0.67 to 0.75.
  • some domains (a domains) oriented in the plane direction rotate so as to be oriented in the thickness direction (direction in which a driving voltage is applied) in the case of application of a driving voltage. Since such 90° domain motion is powerful, the piezoelectricity is further enhanced in a case where this effect is exhibited, and the piezoelectricity is further enhanced than a case where all domains are oriented in the thickness direction.
  • the piezoelectricity can be further enhanced by setting the intensity ratio ⁇ 1 to 0.75 or less and allowing the domains (a domains) oriented in the plane direction to remain at a certain ratio.
  • a lower electrode laminate 11 a in which the lower electrode 14 is formed on the lower protective layer 18 is prepared.
  • the lower electrode laminate 11 a may be prepared by forming a copper thin film or the like as the lower electrode 14 on the surface of the lower protective layer 18 using vacuum vapor deposition, sputtering, plating, or the like.
  • the lower protective layer 18 with a separator, (temporary support) may be used as necessary.
  • a PET having a thickness of 25 ⁇ m to 100 ⁇ m or the like can be used as the separator. The separator may be removed after thermal compression bonding of the upper electrode 16 and the upper protective layer 20 and before lamination of any member on the lower protective layer 18 .
  • a paint is prepared by dissolving a polymer material serving as a material of the matrix in an organic solvent, adding the piezoelectric particles 26 such as PZT particles thereto, and stirring the solution for dispersion.
  • the organic solvent other than the above-described substances is not limited, and various organic solvents can be used.
  • the paint is cast (applied) onto the lower electrode laminate 11 a , and the organic solvent is evaporated and dried.
  • a first laminate 11 b in which the lower electrode 14 is provided on the lower protective layer 18 and the piezoelectric layer 12 is formed on the lower electrode 14 is prepared.
  • the lower electrode 14 indicates an electrode on the base material side in a case where the piezoelectric layer 12 is applied, and does not indicate the vertical positional relationship in the laminate.
  • a casting method of the paint is not limited, and all known methods (coating devices) such as a slide coater or a doctor knife can be used.
  • a dielectric polymer material may be added to the matrix 24 .
  • the polymer material added to the paint may be dissolved.
  • an upper electrode laminate 11 c in which the upper electrode 16 is formed on the upper protective layer 20 is prepared.
  • the upper electrode laminate 11 c may be prepared by forming a copper thin film or the like as the upper electrode 16 on the surface of the upper protective layer 20 using vacuum vapor deposition, sputtering, plating, or the like.
  • the upper electrode laminate 11 c is laminated on the first laminate 11 b such that the upper electrode 16 is oriented to the piezoelectric layer 12 as illustrated in FIG. 4 .
  • a laminate of the first laminate 11 b and the upper electrode laminate 11 c is subjected to the thermal compression bonding using a heating press device, a heating roller pair, or the like such that the upper protective layer 20 and the lower protective layer 18 are sandwiched.
  • the piezoelectric layer 12 is subjected to an electrical polarization treatment (poling) after preparation of the laminate of the first laminate 11 b and the upper electrode laminate 11 c.
  • a method of performing the electrical polarization treatment on the piezoelectric layer 12 is not limited, and a known method can be used.
  • a calender treatment may be performed to smoothen the surface of the piezoelectric layer 12 using a heating roller or the like. By performing the calender treatment, a thermal compression bonding step described below can be smoothly performed.
  • the configuration in which the electrical polarization treatment is performed after the lamination of the upper electrode laminate 11 c on the first laminate 11 b is not limited, and the electrical polarization treatment may be performed before lamination of the upper electrode laminate 11 c.
  • the domains (180° domains) oriented in a direction opposite to the thickness direction which is the direction in which the electric field is applied are switched by the electrical polarization treatment, that is, 180° domain motion is caused so that the directions of domains in the thickness direction can be aligned.
  • a polymer-based piezoelectric composite material film in which the electrode layers and the protective layers are laminated on both surfaces of the piezoelectric layer 12 is prepared by performing the above-described steps.
  • the prepared polymer-based piezoelectric composite material film may be cut into a desired shape according to various applications.
  • Such a polymer-based piezoelectric composite material film may be produced by using a cut sheet-like material or may be prepared by roll to roll (hereinafter, also referred to as RtoR).
  • the treatment 1 is a treatment of performing a polarization treatment by heating the piezoelectric layer 12 in a case of performing the electrical polarization treatment on the piezoelectric layer 12 so that the coefficient of variation of the temperature of the piezoelectric layer 12 during the polarization treatment is set to less than 0.5.
  • the polarization treatment is performed by heating the piezoelectric layer in a case of performing the polarization treatment from the viewpoint of promoting polarization.
  • the temperature of the piezoelectric layer during the electrical polarization treatment is non-uniform in the plane direction and the temperature varies
  • variation in polarization may occur depending on the position of the piezoelectric layer in the plane direction and this may result in non-uniform polarization.
  • Examples of the method of heating the piezoelectric layer in a case of the electrical polarization treatment include a method of using a hot plate, a method of using hot air, and a method of using infrared rays.
  • the temperature is likely to be non-uniform depending on the position.
  • the coefficient of variation of the intensity ratio ⁇ 1 can be set to less than 0.3.
  • the temperature of the piezoelectric layer during the electrical polarization treatment is preferably in a range of 20° C. to 130° C., more preferably in a range of 50° C. to 100° C., and still more preferably in a range of 80° C. to 100° C.
  • the temperature of the piezoelectric layer during the electrical polarization treatment may be estimated indirectly by measuring the surface temperature of the electrode layer or the protective layer using a contact thermometer.
  • the coefficient of variation of the temperature of the piezoelectric layer 12 may be calculated by measuring optional five points of temperatures of the piezoelectric layer with an interval of 10 mm or greater, calculating the average value and the standard deviation thereof, and dividing the standard deviation by the average value.
  • the treatment 2 is a treatment of applying a pressure to the piezoelectric layer 12 in a case where the electrical polarization treatment is performed on the piezoelectric layer 12 .
  • the domains are likely to be aligned by applying the pressure to the piezoelectric layer 12 to perform the electrical polarization treatment, and the coefficient of variation of the intensity ratio ⁇ 1 can be set to less than 0.3.
  • the pressure may be applied to the piezoelectric layer 12 by pressing the laminate of the first laminate 11 b and the upper electrode laminate 11 c from each side of the upper protective layer 20 and the lower protective layer 18 . Further, in a case where the polarization treatment is performed on the first laminate 11 b , the pressure may be applied to the piezoelectric layer 12 by pressing the laminate from each side of the piezoelectric layer 12 and the lower protective layer 18 .
  • the pressure applied to the piezoelectric layer 12 is preferably in a range of 0.3 MPa to 0.9 MPa, more preferably in a range of 0.5 MPa to 0.9 MPa, and still more preferably in a range of 0.6 MPa to 0.8 MPa.
  • the pressure is uniformly applied to the piezoelectric layer 12 in the plane direction.
  • the treatment 3 is a treatment of setting the amplitude of wrinkles formed on the piezoelectric film to be in a range of 1 ⁇ m to 20 ⁇ m.
  • wrinkles may be generated on the piezoelectric film (laminate) in the step of laminating the upper electrode laminate 11 c on the first laminate 11 b .
  • the wrinkles may be generated due to a difference in the Young's modulus and the degree of thermal expansion between layers.
  • the stress is concentrated on the wrinkles in a case where wrinkles are generated on the piezoelectric film. In the portion where the stress is concentrated, depolarization occurs and the aligning properties are degraded.
  • the coefficient of variation of the intensity ratio ⁇ 1 can be set to less than 0.3.
  • Examples of the method of setting the amplitude of the wrinkles formed on the piezoelectric film to be in a range of 1 ⁇ m to 20 ⁇ m include a method of applying a tension to the first laminate 11 b and the upper electrode laminate 11 c and laminating the first laminate 11 b and the upper electrode laminate 11 c while generation of wrinkles is suppressed, in the step of laminating the upper electrode laminate 11 c on the first laminate 11 b.
  • the tension at which generation of wrinkles can be suppressed without damaging the first laminate 11 b and the upper electrode laminate 11 c may be appropriately set depending on the thickness, the material, and the like of the first laminate 11 b and the upper electrode laminate 11 c.
  • the amplitude of wrinkles formed on the piezoelectric film is preferably in a range of 1 ⁇ m to 20 ⁇ m and more preferably in a range of 1 ⁇ m to 10 ⁇ m.
  • the amplitude of the wrinkles formed on the piezoelectric film is measured as follows.
  • the piezoelectric film is cut into a size of 20 mm in the longitudinal direction and 200 mm in the width direction (direction orthogonal to the longitudinal direction) with scissors or the like.
  • the cut piezoelectric film is placed on an XY stage, and the film is fixed at a pressure of 0.6 g/cm 2 by placing weights on regions of 5 mm at both end portions in the width direction.
  • the surface of the piezoelectric film is scanned with a laser displacement meter (measurement range: 100 ⁇ m) in an optional direction and in a direction orthogonal to this optional direction at a speed of 40 mm/s and the amplitude of wrinkles on the surface of the piezoelectric film is measured.
  • the larger value between the measured values in the two directions is defined as the amplitude of wrinkles formed on the piezoelectric film.
  • Such measurement is carried out at optional three points with an interval of 5 mm or greater, and the average value of the amplitudes of wrinkles is acquired.
  • an XY stage BS-2020SG (manufactured by COMS Co., Ltd.) can be used as the XY stage.
  • a laser displacement meter LT-9030M (manufactured by KEYENCE Corporation) can be used as the laser displacement meter.
  • the piezoelectric film is hard. Meanwhile, in a case where the piezoelectric film is extremely hard, there is a concern that the piezoelectric film is less likely to vibrate, and thus the conversion efficiency is decreased. From this viewpoint, the Young's modulus of the piezoelectric film is preferably in a range of 0.5 GPa to 3.5 GPa, more preferably in a range of 0.5 GPa to 2.0 GPa, and still more preferably in a range of 0.8 GPa to 1.5 GPa.
  • a step of performing a mechanical polarization treatment may be performed.
  • the mechanical polarization treatment is a step of applying a shearing stress to the piezoelectric layer 12 of the second laminate 11 d in which the upper electrode laminate 11 c is laminated on the first laminate 11 b .
  • the shearing stress to the piezoelectric layer 12
  • the proportion of the a domains oriented in the plane direction can be decreased, and the proportion of the c domains oriented in the thickness direction can be increased. That is, the intensity ratio ⁇ 1 in the piezoelectric layer can be increased by performing the mechanical polarization treatment.
  • the piezoelectric layer 12 piezoelectric particles 26
  • the piezoelectric particles 26 extend in the vertical direction (thickness direction)
  • 90° domain motion occurs during the extension, and the a domains oriented in the plane direction are set as the c domains oriented in the thickness direction.
  • the orientation of the c domains oriented in the thickness direction does not change. As a result, it is assumed that the proportion of a domains decreases and the proportion of c domain increases.
  • the intensity ratio ⁇ 1 of the (002) plane peak intensity and the (200) plane peak intensity derived from piezoelectric particles in a case where the piezoelectric layer 12 is evaluated by the X-ray diffraction method can be set to 0.6 or greater by performing the mechanical polarization treatment and increasing the proportion of the c domains by decreasing the proportion of the a domains, and thus higher piezoelectricity can be obtained.
  • the mechanical polarization treatment is performed after the electrical polarization treatment.
  • the 90° domain motion occurring due to the mechanical polarization treatment is likely to occur in a case where the 180° domain walls are eliminated.
  • the a domains oriented in the plane direction are allowed to be oriented in the thickness direction and set as the c domains, and thus the proportion of the c domains can be increased by performing the mechanical polarization treatment after a state in which 180° domain motion occurs due to the electrical polarization treatment, 180° domain walls are eliminated, and thus 90° domain motion is likely to occur is prepared.
  • Examples of the method of applying the shearing stress to the piezoelectric layer 12 as the mechanical polarization treatment include a method of pressing a roller from a side of one surface of the second laminate 11 d as illustrated in FIG. 5 .
  • the kind of roller in a case where the shearing stress is applied to the piezoelectric layer 12 using a roller is not particularly limited, and a rubber roller, a metal roller, or the like can be appropriately used.
  • the value of the shearing stress applied to the piezoelectric layer 12 is not particularly limited, and may be appropriately set according to the performance required for the piezoelectric film, the material and thickness of each layer of the piezoelectric film, and the like.
  • the shearing stress applied to the piezoelectric layer 12 may be acquired by dividing the applied shearing load by the cross-sectional area parallel to the shearing load or may be acquired by detecting the tensile strain or the compressive strain generated by the tensile stress or the compressive stress and calculating the shearing stress based on the detection result.
  • the temperature of the piezoelectric film and the roller is set to be preferably in a range of 20° C. to 130° C. and more preferably in a range of 50° C. to 100° C. Since the polymer material is extremely soft and thus the shearing force is unlikely to be applied in a case where the temperature is extremely high, and the polymer material is extremely hard and thus the proportion of domains is unlikely to be changed in a case where the temperature is low, the proportion of domains is considered to be easily changed by holding the temperature at which the polymer material is moderately soft.
  • the piezoelectric film according to the embodiment of the present invention is used in various acoustic devices (audio equipment) such as speakers, microphones, and pickups used in musical instruments such as guitars, to generate (reproduce) a sound from the vibration in response to an electric signal or convert the vibration from a sound into an electric signal.
  • acoustic devices audio equipment
  • speakers microphones
  • pickups used in musical instruments such as guitars
  • the piezoelectric film can also be used in pressure sensitive sensors, power generation elements, and the like in addition to the examples described above.
  • the piezoelectric film may be used as a speaker that generates a sound from the vibration of the film-like piezoelectric film.
  • the piezoelectric film may be used as an exciter that generates a sound by being attached to a vibration plate to vibrate the vibration plate, from the vibration of the piezoelectric film.
  • the present invention will be described in more detail with reference to specific examples of the present invention. Further, the present invention is not limited to the examples, and the materials, the used amounts, the proportions, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed within a range not departing from the scope of the present invention.
  • the lower electrode laminate 11 a and the upper electrode laminate 11 c formed by vacuum-depositing a copper thin film with a thickness of 0.1 ⁇ m on a PET film having a thickness of 4 ⁇ m were prepared. That is, in the present example, the upper electrode 16 and the lower electrode 14 are copper-deposited thin films having a thickness of 0.1 m, and the upper protective layer 20 and the lower protective layer 18 are PET films having a thickness of 4 ⁇ m.
  • a film with a separator temporary support PET having a thickness of 50 ⁇ m was used as the PET film, and the separator of each protective layer was removed after the thermal compression bonding of the upper electrode laminate 11 c.
  • cyanoethylated PVA (CR-V, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in methyl ethyl ketone (MEK) at the following compositional ratio. Thereafter, PZT particles were added to the solution at the following compositional ratio and dispersed using a propeller mixer (rotation speed of 2000 rpm), thereby preparing a paint for forming the piezoelectric layer 12 .
  • PZT particles obtained by sintering commercially available PZT raw material powder at 1000° C. to 1200° C. and crushing and classifying the sintered powder to have an average particle diameter of 5 ⁇ m were used as the PZT particles.
  • the lower electrode 14 (copper-deposited thin film) of the lower electrode laminate 11 a prepared in advance was coated with a paint for forming the piezoelectric layer 12 prepared in advance using a slide coater. Further, the paint was applied such that the film thickness of the coating film after being dried reached 20 ⁇ m.
  • the upper electrode laminate 11 c was laminated on the first laminate 11 b such that the side of the upper electrode 16 (side of the copper thin film) was oriented to the piezoelectric layer 12 , and the laminate was subjected to thermal compression bonding at 120° C.
  • a tension of 5 N/mm 2 was applied to each of the first laminate 11 b and the upper electrode laminate 11 c (treatment 3).
  • the piezoelectric layer 12 and the upper electrode 16 and the lower electrode 14 were adhered to each other, thereby preparing the second laminate 11 d.
  • the electrical polarization treatment was performed on the piezoelectric layer 12 by applying a voltage to a space between the lower electrode 14 and the upper electrode 16 of the second laminate 11 d .
  • the electrical polarization treatment was performed by placing the second laminate 12 d on a hot plate, setting the temperature of the piezoelectric layer 12 to 100° C., and applying a DC voltage of 6 kV to a space between the lower electrode 14 and the upper electrode 16 .
  • the fluctuation of the temperature of the piezoelectric layer 12 was suppressed and the temperature distribution was made uniform by placing the piezoelectric layer after the hot plate was sufficiently heated and covering the piezoelectric layer with a metal flat plate (treatment 1).
  • the coefficient of variation of the temperature of the piezoelectric layer 12 was 0.02.
  • the electrical polarization treatment was performed while the second laminate 11 d was uniformly pressed from the side of the lower protective layer 18 and the upper protective layer 20 side and a pressure was applied to the piezoelectric layer 12 during the electrical polarization treatment (treatment 2).
  • the pressure applied to the piezoelectric layer 12 was 0.7 MPa.
  • the polymer-based piezoelectric composite material film was prepared.
  • the XRD pattern of the crystal structure of the piezoelectric particles 26 in the piezoelectric layer 12 of the prepared piezoelectric film was measured by the X-ray diffraction method (XRD) using an X-ray diffractometer (SmartLab Cu radiation source, manufactured by Rigaku Corporation, 45 kV, 200 mA).
  • XRD X-ray diffraction method
  • SmartLab Cu radiation source manufactured by Rigaku Corporation, 45 kV, 200 mA
  • the piezoelectric film was cut into a size of 40 mm with scissors or the like. Further, 1.5 mol/L of an iron chloride aqueous solution obtained by mixing a ferric chloride hexahydrate and pure water was prepared. The cut piezoelectric film was immersed while being hung in the prepared iron chloride aqueous solution for 12 hours. Thereafter, the immersed piezoelectric film was taken out and washed with pure water several times. The corners of the washed piezoelectric film were held, and the upper electrode laminate was peeled off from the piezoelectric layer at a speed of approximately 4 mm/s to expose the piezoelectric layer.
  • the piezoelectric film from which the upper electrode laminate had been peeled off was washed with pure water several times and naturally dried for 24 hours. In this manner, the electrodes were peeled off from the piezoelectric film, and the XRD measurement was performed on the piezoelectric layer.
  • Such a measurement was performed by measuring optional five points of the intensity ratios and the coefficient of variation was calculated from the average value and the standard deviation of the five points of the intensity ratios ⁇ 1 .
  • the coefficient of variation of the intensity ratio ⁇ 1 was 0.09.
  • the intensity ratio ⁇ 1 (average value) was 0.80.
  • the Young's modulus of the prepared piezoelectric film was 1.2 GPa.
  • the polymer-based piezoelectric composite material film 10 was prepared in the same manner as in Example 1 except that the presence of the treatment 3 in the second lamination step and the presence of the treatment 1 and the treatment 2 in the electrical polarization treatment step were changed as listed in Table 1.
  • the XRD pattern of each of the prepared piezoelectric films was measured in the same manner as in Example 1, and the coefficient of variation of the intensity ratio ⁇ 1 and the intensity ratio ⁇ 1 (average value) were acquired.
  • a polymer-based piezoelectric composite material film was prepared in the same manner as in Example 7 except that the lower electrode laminate 11 a and the upper electrode laminate 11 c formed by vacuum-depositing a copper thin film with a thickness of 0.1 ⁇ m on a polypropylene film having a thickness of 4 ⁇ m were prepared.
  • the XRD pattern of each of the prepared piezoelectric films was measured in the same manner as in Example 1, and the coefficient of variation of the intensity ratio ⁇ 1 and the intensity ratio ⁇ 1 (average value) were acquired.
  • a polymer-based piezoelectric composite material film was prepared in the same manner as in Comparative Example 1 except that the lower electrode laminate 11 a and the upper electrode laminate 11 c formed by vacuum-depositing a copper thin film with a thickness of 0.1 ⁇ m on a polyaramid film having a thickness of 4 ⁇ m were prepared.
  • the XRD pattern of each of the prepared piezoelectric films was measured in the same manner as in Example 1, and the coefficient of variation of the intensity ratio ⁇ 1 and the intensity ratio ⁇ 1 (average value) were acquired.
  • a tensile tester for example, RTF-1310, manufactured by A & D Company, Limited. was used.
  • a measurement sample having a length of 80 mm and a width of 12.8 mm (including a holding part) was cut out from the piezoelectric film with a cutter (craft cutter, product number: XB141, manufactured by OLFA).
  • the top and bottom of the measurement sample were fixed.
  • the distance between gripping jigs was set to 50 mm.
  • the Young's modulus was calculated by the following equation based on the change in stress and the amount of elongation during the measurement.
  • ⁇ N change in stress (N)
  • S cross-sectional area of test piece (mm 2 )
  • ⁇ x amount of elongation
  • L distance between gripping jigs (mm)
  • the stress range was set to be in a range of 0.3N to 5.0N and used for the calculation of the change in stress ( ⁇ N) and the amount of elongation ( ⁇ x) at this time.
  • a sheet in which a 30 ⁇ m silicon oxide film was vapor-deposited on both surfaces of a PET film having a thickness of 200 ⁇ m was cut into an A4 size and prepared as a vibration plate.
  • the prepared electroacoustic conversion film was cut into a size of 5 cm ⁇ 10 cm, double-sided tape having a thickness of 10 ⁇ m was attached to the entire one surface side, and the film was attached to the central portion of an A4-sized vibration plate. Next, both short sides of the A4-sized vibration plate were fixed to a plastic rod to prepare an electroacoustic converter.
  • the vibration plate may be scraped off to take out the electroacoustic conversion film in the following manner.
  • MINICOM manufactured by Tokyo Semitsu Co., Ltd.
  • the electroacoustic converter was fixed onto the milling machine using a FIX FILM (manufactured by Fujicopian Co., Ltd.).
  • the vibration plate was cut with a milling machine, and the electroacoustic conversion film from which the vibration plate was removed was taken out.
  • the confirmation of whether the vibration plate was removed from the electroacoustic converter and the electroacoustic conversion film was able to be taken out was carried out based on whether the thickness of the layer including the electroacoustic conversion film remaining after the milling was in a range of (“thickness of electroacoustic converter acquired above” ⁇ “thickness of vibration plate acquired above”) ⁇ 5 ⁇ m.
  • the thickness of the electroacoustic conversion film here is in the range defined above, a trace amount of residues of the vibration plate and the double-sided tape for adhering the vibration plate and the electroacoustic conversion film may remain.
  • the level of the sound pressure of the prepared electroacoustic converter was measured, and the sound pressure sensitivity was acquired.
  • the level of the sound pressure was measured and converted into the sound pressure sensitivity by disposing a microphone P at a position separated from the center of the piezoelectric film of the electroacoustic converter by 0.5 m and inputting a 1 W sine wave with a frequency of 1 kHz to a space between the upper electrode and the lower electrode of the electroacoustic converter.
  • the amplitude of the wrinkles formed on the piezoelectric film is preferably 20 ⁇ m or less.

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JP5716263B2 (ja) * 2008-06-30 2015-05-13 日立金属株式会社 セラミックス焼結体および圧電素子
JP6043673B2 (ja) * 2013-03-29 2016-12-14 富士フイルム株式会社 電気音響変換用高分子複合圧電体
WO2017018313A1 (ja) * 2015-07-27 2017-02-02 富士フイルム株式会社 電気音響変換フィルムおよびその製造方法、ならびに、電気音響変換器、フレキシブルディスプレイ、声帯マイクロフォンおよび楽器用センサー

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